U.S. patent application number 14/838202 was filed with the patent office on 2015-12-24 for method and system for graphene formation.
The applicant listed for this patent is CALIFORNIA INSTITUTE OF TECHNOLOGY. Invention is credited to David A. Boyd.
Application Number | 20150368111 14/838202 |
Document ID | / |
Family ID | 49006226 |
Filed Date | 2015-12-24 |
United States Patent
Application |
20150368111 |
Kind Code |
A1 |
Boyd; David A. |
December 24, 2015 |
METHOD AND SYSTEM FOR GRAPHENE FORMATION
Abstract
A system for graphene production includes a plurality of gas
sources, a plurality of mass flow controllers, and a processing
chamber. The system also includes a plasma source operable, a
vacuum pump, a processor, and a non-transitory computer-readable
storage medium including a plurality of computer-readable
instructions. The plurality of instructions include instructions
that cause the data processor to subject a substrate to a reduced
pressure environment, to provide a carrier gas and a carbon source,
and to expose at least a portion of the substrate to the carrier
gas and the carbon source. The plurality of instructions also
include instructions that cause the data processor to perform a
surface treatment process on the at least a portion of the
substrate and to convert a portion of the carbon source to graphene
disposed on the at least a portion of the substrate.
Inventors: |
Boyd; David A.; (La Canada,
CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
CALIFORNIA INSTITUTE OF TECHNOLOGY |
Pasadena |
CA |
US |
|
|
Family ID: |
49006226 |
Appl. No.: |
14/838202 |
Filed: |
August 27, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13774188 |
Feb 22, 2013 |
9150418 |
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14838202 |
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61603104 |
Feb 24, 2012 |
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61607337 |
Mar 6, 2012 |
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61677323 |
Jul 30, 2012 |
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Current U.S.
Class: |
118/697 |
Current CPC
Class: |
B01J 19/088 20130101;
B01J 2219/0894 20130101; B01J 19/22 20130101; B82Y 40/00 20130101;
C23C 16/0245 20130101; C23C 16/52 20130101; B01J 2219/0879
20130101; H01J 37/32522 20130101; H01J 37/32816 20130101; C23C
16/545 20130101; B82Y 30/00 20130101; H01L 21/02425 20130101; H01L
21/02527 20130101; H01L 21/0262 20130101; H01J 2237/335 20130101;
C01B 32/186 20170801; H01J 37/32449 20130101; C23C 16/26 20130101;
H01L 21/02046 20130101; H01J 37/32082 20130101; H01L 29/1606
20130101; H01L 21/02661 20130101; H01L 29/32 20130101 |
International
Class: |
C01B 31/04 20060101
C01B031/04; H01J 37/32 20060101 H01J037/32; C23C 16/52 20060101
C23C016/52 |
Claims
1. A system for graphene production, the system comprising: a
plurality of gas sources; a plurality of mass flow controllers,
each of the plurality of mass flow controllers coupled to one of
the plurality of gas sources; a processing chamber in fluid
communication with the plurality of mass flow controllers; a plasma
source operable to form a plasma in the processing chamber; a
vacuum pump in fluid communication with the processing chamber; a
processor; and a non-transitory computer-readable storage medium
comprising a plurality of computer-readable instructions tangibly
embodied on the computer-readable storage medium, which, when
executed by a data processor, provide for graphene production, the
plurality of instructions comprising: instructions that cause the
data processor to subject a substrate to a reduced pressure
environment; instructions that cause the data processor to provide
a carrier gas and a carbon source; instructions that cause the data
processor to expose at least a portion of the substrate to the
carrier gas and the carbon source; instructions that cause the data
processor to perform a surface treatment process on the at least a
portion of the substrate; and instructions that cause the data
processor to convert a portion of the carbon source to graphene
disposed on the at least a portion of the substrate.
2. The system of claim 1 wherein the substrate comprises a copper
foil.
3. The system of claim 1 wherein the carrier gas comprises
hydrogen.
4. The system of claim 3 wherein the surface treatment process
comprises an RF hydrogen plasma.
5. The system of claim 1 wherein the surface treatment process
comprises an RF hydrogen plasma cleaning process.
6. The system of claim 1 wherein the carbon source comprises at
least one of methane, ethane, propane, or butane.
7. The system of claim 1 wherein the carbon source comprises
methane.
8. The system of claim 1 wherein providing the carrier gas and
providing the carbon source are performed concurrently.
9. The system of claim 1 wherein the reduced pressure is less than
500 mTorr.
10. The system of claim 1 wherein a ratio of a first Raman peak
associated with defects to a second Raman peak associated with
graphite is less than one.
11. The system of claim 1 wherein the carbon source comprises less
than 0.1% of a combined carrier gas and carbon source flow.
12. The system of claim 1 wherein the surface treatment process is
performed at a pressure less than or equal to 500 mTorr.
13. The system of claim 1 wherein the reduced pressure environment
includes at least one atmospheric gas.
14. The system of claim 13 wherein the at least one atmosphier gas
comprises nitrogen.
Description
CROSS-REFERENCES TO RELATED APPLICATIONS
[0001] This application is a divisional of U.S. patent application
Ser. No. 13/774,188, filed on Feb. 22, 2013, entitled "Method and
System for Graphene Formation," which claims priority to U.S.
Provisional Patent Application No. 61/603,104, filed on Feb. 24,
2012, entitled "Method for Forming Graphene at Reduced Processing
Temperatures," U.S. Provisional Patent Application No. 61/607,337,
filed on Mar. 6, 2012, entitled "Method for Forming Graphene at
Reduced Processing Temperatures," and U.S. Provisional Patent
Application No. 61/677,323, filed on Jul. 30, 2012, entitled
Single-Step Method for Forming High Quality, Large Area Graphene at
Reduced Temperature," the disclosures of which are hereby
incorporated by reference in their entirety for all purposes.
BACKGROUND OF THE INVENTION
[0002] Graphene is an allotrope of carbon in which the atoms are
arrayed in a single atom sheet in a regular hexagonal pattern. The
electronic properties of graphene differ from conventional three
dimensional materials and graphene can be considered as a zero
bandgap semiconductor. Graphene can have a high carrier mobility at
room temperature, making graphene a candidate material for
electronic circuit applications.
[0003] Current methods of forming graphene films include chemical
vapor deposition (CVD) at high temperatures, for example,
1,000.degree. C. CVD growth techniques may also include pre-growth
exposure to hydrogen at high temperatures (e.g.,
.about.1,000.degree. C.).
[0004] Despite the progress made related to the formation of
graphene films, there is a need in the art for improved methods and
systems related to graphene production.
SUMMARY OF THE INVENTION
[0005] The present invention relates generally to methods and
systems for material synthesis. More specifically, the present
invention relates to methods and systems for growing high quality,
large area graphene. Merely by way of example, the invention has
been applied to a method of growing graphene at room temperature
under a reduced pressure atmosphere. The methods and techniques can
be applied to a variety of graphene growth systems including CMOS
compatible semiconductor growth processes.
[0006] According to an embodiment of the present invention, a
method of forming a film of graphene is provided. The method
includes placing a substrate in a processing chamber at a reduced
pressure and performing a surface treatment process on at least a
portion of the substrate. The method also includes providing a
carbon containing material in the processing chamber and exposing
the substrate to the carbon containing material. The method further
includes converting a portion of the carbon containing material to
a film of graphene on the substrate.
[0007] According to another embodiment of the present invention, a
method for forming graphene is provided. The method includes
providing a substrate and subjecting the substrate to a reduced
pressure environment. The method also includes providing a carrier
gas and a carbon source and exposing at least a portion of the
substrate to the carrier gas and the carbon source. The method
further includes performing a surface treatment process on the at
least a portion of the substrate and converting a portion of the
carbon source to graphene disposed on the at least a portion of the
substrate.
[0008] According to a particular embodiment of the present
invention, a system for graphene production is provided. The system
includes a plurality of gas sources, a plurality of mass flow
controllers, each of the plurality of mass flow controllers coupled
to one of the plurality of gas sources, and a processing chamber in
fluid communication with the plurality of mass flow controllers.
The system also includes a plasma source operable to form a plasma
in the processing chamber and a vacuum pump in fluid communication
with the processing chamber. The system further includes a
processor and a non-transitory computer-readable storage medium
comprising a plurality of computer-readable instructions tangibly
embodied on the computer-readable storage medium, which, when
executed by a data processor, provide for graphene production. The
plurality of instructions include instructions that cause the data
processor to subject a substrate to a reduced pressure environment
and instructions that cause the data processor to provide a carrier
gas and a carbon source. The plurality of instructions also include
instructions that cause the data processor to expose at least a
portion of the substrate to the carrier gas and the carbon source
and instructions that cause the data processor to perform a surface
treatment process on the at least a portion of the substrate. The
plurality of instructions further include instructions that cause
the data processor to convert a portion of the carbon source to
graphene disposed on the at least a portion of the substrate.
[0009] Numerous benefits are achieved by way of the present
invention over conventional techniques. For example, embodiments of
the present invention provide techniques for producing graphene
without the need for a furnace. Additionally, as described herein,
graphene growth can be achieved more rapidly than provided by
conventional techniques. Moreover, the low thermal budget processes
described herein enable the growth of graphene characterized by
lower stress than that observed in graphene grown using
conventional methods. Some embodiments of the present invention
provide methods and systems for producing graphene without the use
of a furnace, enabling growth to be achieved at a more rapid rate
than using conventional techniques, significantly reducing growth
times (e.g., from 5 hours to 15 minutes) while producing low stress
graphene films. These and other embodiments of the invention along
with many of its advantages and features are described in more
detail in conjunction with the text below and attached figures.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 is a simplified schematic diagram illustrating a
system for graphene production according to an embodiment of the
present invention;
[0011] FIG. 2 is a simplified flowchart illustrating a method of
growing graphene according to an embodiment of the present
invention;
[0012] FIG. 3 shows data for a graphene film grown using
conventional techniques and for a graphene film grown using an
embodiment of the present invention;
[0013] FIG. 4 is a simplified flowchart illustrating a method of
growing graphene according to another embodiment of the present
invention;
[0014] FIG. 5 shows data for a graphene film grown using
conventional techniques and for a graphene film grown using another
embodiment of the present invention;
[0015] FIG. 6 is a simplified flowchart illustrating a method of
growing graphene according to yet another embodiment of the present
invention;
[0016] FIG. 7 shows data for a graphene film grown using
conventional techniques and for a graphene film grown using an
embodiment of the present invention; and
[0017] FIG. 8 is a simplified schematic diagram of a continuous
roll-to-roll system for graphene production according to an
embodiment of the present invention.
DETAILED DESCRIPTION OF SPECIFIC EMBODIMENTS
[0018] The present invention relates generally to methods and
systems for material synthesis. More specifically, the present
invention relates to methods and systems for growing high quality,
large area graphene. Merely by way of example, the invention has
been applied to a method of growing graphene at room temperature
under a reduced pressure atmosphere. The methods and techniques can
be applied to a variety of graphene growth systems including CMOS
compatible semiconductor growth processes.
[0019] According to embodiments of the present invention, methods
and systems for graphene production are provided. In an embodiment,
the process includes subjecting a substrate (e.g., a copper foil)
to a hydrogen plasma prior to the introduction of carbon
precursors. This process is performed under a reduced pressure
atmosphere. This process avoids the high temperature hydrogen
anneal utilized in conventional graphene growth. Accordingly, the
present invention enables the growth of high quality graphene at
low temperature (e.g., room temperature) to enable low temperature
processing without either pre-growth high temperature annealing in
hydrogen or high temperatures during growth.
[0020] The high processing temperatures (e.g., .about.1,000.degree.
C.) utilized in conjunction with conventional methods for forming
graphene by CVD ultimately produce adverse consequences for device
performance. Lower thermal budgets are desirable, reducing energy
costs for production and potentially producing graphene films with
reduced stress. Additionally, lower thermal budgets can open up new
avenues for device integration. High processing temperatures are
conventionally used either during hydrogen annealing performed
prior to growth and during CVD growth. For CVD growth on copper
films, annealing in hydrogen is believed to clean the copper
surface by removing the native copper oxide layer and providing
access to elemental copper on which the graphene layer grows. The
substrate cleaning produced during a high temperature hydrogen
anneal is evidenced by the build-up of copper on the inside of the
processing tube.
[0021] An alternative method for cleaning a surface is through the
use of a plasma (e.g., a microwave plasma), which enables substrate
cleaning to be performed without the application of high
temperature to the processing environment. Without limiting
embodiments of the present invention, the inventor believes that
the energetic species in the plasma serve to remove the native
oxide layer present on the copper substrate.
[0022] According to an embodiment of the present invention, a
method for growing high quality graphene using a lower thermal
budget process compared to conventional methods is provided. In
this embodiment, the conventional high temperature hydrogen anneal
is replaced with a room temperature plasma clean before the start
of the CVD growth. Accordingly, the overall thermal budget of the
process is reduced in comparison with conventional techniques.
[0023] FIG. 1 is a simplified schematic diagram illustrating a
system for graphene production according to an embodiment of the
present invention. The system includes a processing chamber 110.
The processing chamber can also be referred to as a processing
tube. The processing chamber is fabricated from materials such as
quartz that provide a non-reactive environment that will sustain
plasma generation. In addition to quartz, other materials,
including alumina, glass, and the like can be utilized in
fabricating the processing chamber. An RF plasma generator 120
(e.g., an Evenson cavity suitable for generating a microwave
plasma) and an associated power supply 122 are provided in order to
generate an RF plasma (e.g., a microwave plasma in the ultra high
frequency (UHF) portion of the RF spectrum) in a portion of the
processing chamber. The portion of the processing chamber can
include all or a fraction of the processing chamber depending on
the particular implementation.
[0024] Gas sources 130, 132, and 134 are illustrated in FIG. 1 and
can include fewer or a greater number of sources. In the
illustrated embodiment, the gas sources are H.sub.2, Ar, and
CH.sub.4 although the present invention is not limited to these
particular gases. Mass flow controllers (MFCs) 131, 133, and 135 or
other suitable flow controllers are utilized to control the flow
rate of the gases from the gas sources to the processing
chamber.
[0025] A leak valve 139 is illustrated in FIG. 1 and can be used to
control the flow of the carbon source at levels below that provided
by MFCs. In some embodiments, MFC 135 is operated in an open
condition and the flow of the carbon source can be controlled using
a feedback loop incorporating a feedback signal from optical
spectrometer 160. Alternatively, a pre-mixture of H.sub.2 and
CH.sub.4 (or other suitable carbon source) could be utilized.
Accordingly, some embodiments utilize the optical emission spectra
to adjust the amount of the carbon source (e.g., methane) in the
stream since the optical emission spectra can be sensitive to very
small changes in the position of the leak valve.
[0026] In order to monitor the pressure in the processing chamber
110, one or more pressure gauges 140 and 142 can be utilized in the
vacuum lines leading to the foreline trap 144 and the vacuum pump
146. Additional vacuum elements can be utilized as appropriate to
the particular application. Additionally, one or more vacuum
control valves 148 can be utilized to control the pressure in the
processing chamber.
[0027] In order to provide for characterization of the processing
environment and the graphene formation process, an optical
spectrometer 160 is provided, illustrated as optically coupled to
the processing chamber using a fiber optic cable 162. In addition
to optical emission spectrometers (OES), which can be used to
control and adjust the amount of the carbon source in the flow
stream, the OES can be used to measure the emission peaks. In some
embodiments, a ratio of a set of emission peaks can be used to
monitor the growth process and produce consistent results. In other
implementations, an optical pyrometer is used to measure the sample
temperature. In some embodiments, an optical inspection system (for
example, a mirror that provides optical access to one or more
surfaces of the substrate) is utilized during growth to
characterize the state of copper removal. Thus, in addition to an
optical spectrometer, other optical inspection techniques are
included within the scope of the present invention.
[0028] A computer 170 including a processor 172 and computer
readable medium 174 is provided and coupled to the MFCs, the vacuum
control valve 148, the RF plasma generator 120 and power supply
122, the optical emission spectrometer (OES) 160, and other
suitable system components in order to provide for control of the
various system components. In some implementations, fewer or more
components can be coupled to the computer. The processor 172 is
used to perform calculations related to controlling at least some
of the vacuum pressure, gas flow rates, plasma generation, and
other system parameters. A computer readable medium 174 (also
referred to as a database or a memory) is coupled to the processor
172 in order to store data used by the processor and other system
elements. The processor 172 interacts with the optical spectrometer
160 in some embodiments, which provides data on the state of the
substrate cleaning process, graphene deposition process, and the
like. Using the processor 172, the memory 174, and the I/O
interface 176, a user is able to operate the system to form
graphene as described herein.
[0029] The processor 172 can be a general purpose microprocessor
configured to execute instructions and data, such as a Pentium
processor manufactured by the Intel Corporation of Santa Clara,
Calif. It can also be an Application Specific Integrated Circuit
(ASIC) that embodies at least part of the instructions for
performing the method in accordance with the present invention in
software, firmware and/or hardware. As an example, such processors
include dedicated circuitry, ASICs, combinatorial logic, other
programmable processors, combinations thereof, and the like.
[0030] The memory 174 can be local or distributed as appropriate to
the particular application. Memory 174 may include a number of
memories including a main random access memory (RAM) for storage of
instructions and data during program execution and a read only
memory (ROM) in which fixed instructions are stored. Thus, memory
174 provides persistent (non-volatile) storage for program and data
files, and may include a hard disk drive, flash memory, a floppy
disk drive along with associated removable media, a Compact Disk
Read Only Memory (CD-ROM) drive, an optical drive, removable media
cartridges, and other like storage media.
[0031] FIG. 2 is a simplified flowchart illustrating a method of
growing graphene according to an embodiment of the present
invention. The method includes placing a substrate in a reduced
pressure environment (210). In an embodiment, the substrate is a
copper foil (e.g., 0.025 mm in thickness) and the reduced pressure
environment is a vacuum environment (e.g., pressure in the range of
25 mTorr to 0.5 Torr). In some embodiments, the total system
pressure is between 25 mTorr and 40 mTorr, but can be lower
depending on the particular vacuum systems utilized. During
processing, the pressure is maintained at 500 mTorr in some
implementations as described more fully herein.
[0032] The method also includes subjected the substrate to a flow
of cleaning gas (e.g., hydrogen) (212) and forming an RF plasma in
the vicinity of the substrate for a predetermined period of time
(214). In some embodiments, the temperature of the substrate during
RF plasma cleaning is at reduced temperatures compared to the
conventional 1,000.degree. C. hydrogen anneal, for example, at or
near room temperature. Thus, embodiments of the present invention
enable low temperature processing not available using conventional
techniques.
[0033] After the RF plasma is extinguished, the sample is heated to
a growth temperature (e.g., 800.degree. C.) (216). In some
embodiments, during the heating process, the substrate is
maintained under vacuum conditions with hydrogen flowing to
preserve the substrate in an inert environment. Without limiting
embodiments of the present invention, the inventor believes that
the RF plasma increases the reactivity of the substrate, thereby
preparing the substrate for subsequent growth when exposed to
carbon containing materials. It should be noted that in some
implementations, the vacuum environment (e.g., from 25 mTorr to 0.5
Torr) is such that gases from the ambient atmosphere (including
air, nitrogen, and the like) may be present since an ultrahigh
vacuum environment is not required by some embodiments. For
increased control of the vacuum environment, additional control of
the gases present in the processing chamber can be provided as will
be evident to one familiar with CVD systems.
[0034] The method further includes subjecting the substrate to a
flow of a carbon precursor for a predetermined period of time
(218). As an example, the carbon precursor can be one of several
gaseous species, including methane, acetylene, cyclohexane,
toluene, PMMA, polystyrene, benzene, a combination thereof, or the
like. After growth, the substrate is cooled and removed from the
growth chamber.
[0035] It should be appreciated that the specific steps illustrated
in FIG. 2 provide a particular method of growing graphene according
to an embodiment of the present invention. Other sequences of steps
may also be performed according to alternative embodiments. For
example, alternative embodiments of the present invention may
perform the steps outlined above in a different order. Moreover,
the individual steps illustrated in FIG. 2 may include multiple
sub-steps that may be performed in various sequences as appropriate
to the individual step. Furthermore, additional steps may be added
or removed depending on the particular applications. One of
ordinary skill in the art would recognize many variations,
modifications, and alternatives.
[0036] Utilizing embodiments of the present invention as discussed
in relation to FIG. 2, graphene growth on copper foils has been
performed at growth temperatures ranging from about 800.degree. C.
to about 1,000.degree. C. Accordingly, growth at temperatures lower
than conventional graphene growth temperatures are provided by some
embodiments of the present invention. FIG. 3 shows data (i.e.,
spectral data collected using Raman spectroscopy) for a graphene
film grown using conventional techniques (plot A) and for a
graphene film grown using the method discussed in relation to FIG.
2 (plot B). As illustrated in FIG. 3, the graphene grown on single
crystal copper at 1,000.degree. C. (plot A) and the graphene grown
on copper foil using a low temperature plasma clean process
followed by 800.degree. C. growth (plot B) are characterized by the
two sharp features of the Raman spectra at .about.1580 and 2700
cm.sup.-1 and the absence of a pronounced defect peak at
.about.1350 cm.sup.-1, indicating that embodiments of the present
invention produce a high quality graphene film utilizing the plasma
assist conditions described herein.
[0037] In some embodiments utilizing a two-step clean/growth
process, the substrate is maintained in an inert environment during
the time between the plasma treatment used to clean the surface and
the exposure to the carbon source during growth. The ability to
keep the substrate in this inert environment (e.g., maintain the
process under vacuum) enables the treated surface to remain in the
treated state since copper quickly forms an oxide when exposed to
oxygen.
[0038] Utilizing the system illustrated in FIG. 1, graphene was
formed as follows. An RF plasma was formed in the processing
chamber in the vicinity of the substrate (a copper foil) using an
Evenson cavity with an input power of 40 W for a period of 15
minutes with a flow rate of hydrogen of 2 sccm. During the
application of the RF plasma, a significant amount of copper was
observed in the vicinity of the microwave cavity, indicating that
the RF plasma was etching or otherwise removing copper from the
substrate. The RF plasma was extinguished and the substrate was
heated under a flow of 2 sccm of hydrogen at 42 mTorr to
800.degree. C.
[0039] Subsequently, a flow of CH.sub.4 was added at a flow rate of
35 sccm and the total pressure in the processing chamber was
increased to 500 mTorr. After 15 minutes of these conditions, the
substrate was cooled under the same flow and pressure. Upon
cooling, the substrate was removed and Raman spectroscopy was
performed (plot A in FIG. 5), demonstrating that graphene had been
formed on the backside of the substrate adjacent the susceptor,
which can also be referred to as a sample holder. This procedure
was repeated at growth temperatures of 700.degree. C. and
600.degree. C. with similar results. In addition to single layers
of graphene, embodiments of the present invention are useful for
forming other isomorphs of carbon, including multi-layer graphene,
carbon nanotubes (e.g., using a VLS process), diamond like carbon,
graphite, amorphous carbon, Bucky Balls, and the like. One of
ordinary skill in the art would recognize many variations,
modifications, and alternatives.
[0040] FIG. 4 is a simplified flowchart illustrating a method of
growing graphene according to another embodiment of the present
invention. The method shares some similar processes with the
graphene growth process associated with the Raman spectra in plot A
of FIG. 5 and the description related to this high temperature
(e.g., 800.degree. C.) growth process is applicable to the growth
process illustrated in FIG. 4 as appropriate.
[0041] The method includes providing a substrate in a processing
chamber at a reduced pressure environment (410). In an embodiment,
the substrate can be a copper foil or other suitable substrate and
the reduced pressure environment can be a vacuum environment in the
processing chamber 110 illustrated in FIG. 1, for example,
pressures ranging from about 1 to about 500 mTorr. The pressure can
be less than 500 mTorr in some implementations. In some
embodiments, the method also includes introducing a flow of
hydrogen gas into the processing chamber (412), for example, at a
flow rate of 2 sccm. Other gases can also be utilized, including
nitrogen, argon, other noble gases, chlorine, other halogens,
mixtures of these gases (e.g., chlorine and argon), and the like.
Although the gas is flowing through the processing chamber, the
application of vacuum to the chamber is sufficient to maintain the
reduced pressure environment despite the gas flow. In some
embodiments, the pressure in the processing chamber is maintained
at a predetermined pressure value, for example, 500 mTorr, for a
predetermined time. In order to effectively remove native oxides,
the partial pressure of oxygen in the reduced pressure environment
can be less than 30 mTorr, the partial pressure of hydrogen in the
reduced pressure environment can be less than 500 mTorr, and the
partial pressure of inert gases and/or atmospheric gases including
water vapor in the reduced pressure environment can be less than
500 mTorr. In other embodiments, the partial pressure of air in the
reduced pressure environment can be less than 30 mTorr, the partial
pressure of water in the reduced pressure environment can be less
than 30 mTorr, or the partial pressure of the carrier gas and the
carbon source in the reduced pressure environment can be less than
500 mTorr. In a particular embodiment, the total pressure of the
carrier gas and the carbon source in the reduced pressure
environment is less than 500 mTorr. One of ordinary skill in the
art would recognize many variations, modifications, and
alternatives.
[0042] Additionally, the method includes initiating an RF plasma in
the processing chamber (414) and subjecting the substrate to the RF
plasma for a predetermined period of time (416). During the
exposure to the RF plasma, the substrate surface is cleaned and/or
treated to remove native oxides and prepare the surface for
deposition of the graphene. During the RF plasma treatment, the
substrate is maintained in a reduced pressure environment, for
example, by maintaining vacuum conditions. As an example, the RF
plasma (e.g., an RF hydrogen plasma formed in conjunction with the
flow of hydrogen in the processing chamber) can be formed in the
processing chamber in the vicinity of the substrate (a copper foil)
using an Evenson cavity with an input power of 40 W for a period of
15 minutes (e.g., with a flow rate of hydrogen of 2 sccm). During
the application of the RF plasma, a significant amount of copper
was observed in the vicinity of the microwave cavity, indicating
that the RF plasma was etching or otherwise removing copper from
the substrate.
[0043] After the RF plasma treatment, the plasma is extinguished
and the substrate is maintained in a reduced pressure environment,
for example, in a low pressure hydrogen environment, with a flow
rate of H.sub.2 of 2 sccm, resulting in a pressure of 42 mTorr. The
method further includes flowing a carbon precursor (e.g., methane)
into the processing chamber (418), for example, at a flow rate of
35 sccm of CH.sub.4, producing a pressure in the processing chamber
of 500 mTorr. Thus, a reduced pressure atmosphere can be maintained
while the substrate is exposed to the carbon containing material in
some embodiments, for example, at a pressure less than 500 mTorr.
The temperature during the flow of the carbon precursor can be room
temperature, temperatures below room temperature, or temperatures
above room temperature. In a particular embodiment, the temperature
during the flow of the carbon precursor is between 20.degree. C.
and 30.degree. C., for example, room temperature.
[0044] During the flow of the carbon precursor, the pressure in the
chamber can be held at a prescribed value (e.g., 42 mTorr) or
varied as a function of time depending on the particular
application. In some embodiments, a reduced pressure environment is
maintained during the flow of the carbon precursor. The flow of the
carbon precursor results in the deposition of graphene on the
substrate according to embodiments of the present invention, for
example, at room temperature. The graphene can be formed on one
side or both sides of the substrate depending on the deposition
conditions. In some implementations, a cover or cap is utilized in
close proximity to the substrate to enhance graphene growth.
Without limiting embodiments of the present invention, the inventor
believes that the use of a cover or cap can increase the residence
time of the species and/or precursors adjacent the substrate
surface, impacting the reaction kinetics and thereby increasing the
deposition rate. In some embodiments, graphene growth on the
backside of the substrate adjacent the susceptor or sample holder
is observed. Such enhancements in the graphene growth may be
attributed to the low velocity of the methane flow between the
substrate and susceptor or sample holder and the corresponding long
residence time in comparison with other surfaces that are not
covered or capped. Alternatively, the concentration of the carbon
source in the gas flow can be decreased to limit the amount of
carbon available at the growth surface, thereby enhancing graphene
growth.
[0045] After a predetermined period of time, the flow rates of the
hydrogen and the carbon precursor are decreased, for example, to
zero. Because the processing chamber is in communication with
vacuum pumps, the processing chamber is evacuated and can be
back-filled with argon or other suitable inert gases. Subsequently,
the substrate can be removed from the processing chamber to
characterize the deposited graphene. In some embodiments, the total
pressure is increased to 500 mTorr during all or a portion of the
methane flow, which can be maintained for a period such as 15
minutes. After graphene formation, the processing chamber can be
filled with argon or other suitable inert gases prior to removal of
the substrate for characterization.
[0046] As illustrated in FIG. 4, after the substrate is placed in a
reduced pressure environment, an optional flow of hydrogen gas
(412) can be used in generating an RF hydrogen plasma in the
processing chamber (414).
[0047] It should be appreciated that the specific steps illustrated
in FIG. 4 provide a particular method of growing graphene according
to an embodiment of the present invention. Other sequences of steps
may also be performed according to alternative embodiments. For
example, alternative embodiments of the present invention may
perform the steps outlined above in a different order. Moreover,
the individual steps illustrated in FIG. 4 may include multiple
sub-steps that may be performed in various sequences as appropriate
to the individual step. Furthermore, additional steps may be added
or removed depending on the particular applications. One of
ordinary skill in the art would recognize many variations,
modifications, and alternatives.
[0048] FIG. 5 shows data for a graphene film grown using
conventional techniques and for a graphene film grown using another
embodiment of the present invention. As illustrated in FIG. 5, the
Raman spectra for graphene grown using conventional techniques
(i.e., single crystal copper substrate with growth performed at
1,000.degree. C. is plotted as plot A. Plot B illustrates the Raman
spectra for graphene formed on a copper foil after plasma cleaning
followed by growth at 800.degree. C. Plot C illustrates the Raman
spectra for graphene formed on copper foil using the method
illustrated in FIG. 4, i.e., an RF plasma clean process followed by
room temperature deposition of the graphene. The graphene films
used for the data collection in FIG. 5 were all grown using 35 sccm
of CH.sub.4 and 2 sccm of H.sub.2, with a growth time of 15 minutes
under 500 mTorr total pressure. As illustrated in FIG. 5, the
graphene grown at room temperature (i.e., 24.degree. C. and
800.degree. C. have similar Raman spectra to graphene grown by
thermal CVD at 1,000 C. The two sharp features of the Raman spectra
at .about.1580 and 2700 cm.sup.-1 and the absence of a pronounced
defect peak at 1350 cm.sup.-1 indicate that both films are of good
quality.
[0049] Some embodiments of the present invention utilize one of
several methods to treat the substrate surface prior to growth. As
an example, a copper foil substrate can be cleaned using low
temperature processes, producing a build-up of copper on the inside
of the quartz processing tube, which is evidence of copper removal
from the foil during the cleaning process and preparation of the
growth surface for graphene production. In some embodiments,
metrology can be performed to measure the level of copper
deposition on the inside of the processing chamber, for example,
near the substrate, and thereby determine the status of the
substrate and/or as a result of the Evenson cavity plasma
treatment. One substrate cleaning process utilizes an RF hydrogen
plasma created adjacent the copper surface. As will be evident to
one of skill in the art, an RF plasma is a vacuum process that
ionizes gas molecules with high frequency voltages. The energetic
and reactive species in the plasma can then serve to clean or etch
a surface by removing the native surface layer or surface
contaminants. Some embodiments of the present invention utilize a
low temperature RF plasma process that does not entail the high
temperatures normally associated with a hydrogen anneal.
[0050] In one implementation, an Evenson cavity was used as the
plasma source, with an excitation frequency of 2450 MHz. The
Evenson cavity can excite discharges in both static and flowing
gases at pressures ranging from a few mTorr to several hundred
Torr. A benefit of this particular RF microwave cavity is that it
can be placed directly on a quartz vacuum tube to generate a plasma
in situ.
[0051] In addition to copper substrates, other substrates are
suitable for use with embodiments of the present invention,
including nickel, platinum, iron, aluminum, cobalt, ruthenium,
magnesium oxide, alloys of these materials, silicon, silicon
carbide, combinations thereof, and the like.
[0052] In addition to the use of RF plasmas for pre-growth or
one-step growth surface treatment, other surface preparation
methods can be utilized, including chemical methods such as an acid
etch; mechanical methods such as physical machining, ion beam
bombardment, ultrasonic cleaning, polishing, laser ablation,
abrasion, physical etching; chemi-mechanical methods such as
reactive ion etching, electropolishing, argon plasma etching;
electronic methods such as electron beam exposure, electron beam
heating, inductive heating, joule heating; and electrochemical
methods.
[0053] FIG. 6 is a simplified flowchart illustrating a method of
growing graphene according to yet another embodiment of the present
invention. The graphene formation method illustrated in FIG. 6
shares some similarities with the method of graphene formation
illustrated in FIG. 4. Accordingly, description related to the
method illustrated in FIG. 4 is applicable to the processes and
materials described in relation to FIG. 6 as appropriate. One of
ordinary skill in the art would recognize many variations,
modifications, and alternatives.
[0054] As illustrated in FIG. 6, embodiments of the present
invention provide a method for growing high quality, large area
graphene (e.g., a graphene film) at reduced temperature in a single
step. In summary, the method includes subjecting a substrate (e.g.,
a copper foil) to a hydrogen plasma containing trace amounts of
methane. The process is performed in a reduced pressure
environment. Beneficially, the process avoids the high temperature
hydrogen anneal used in conventional graphene growth and the
associated multiple processing steps. In this manner, growth of
high quality graphene can occur in one step, at reduced
temperatures, and without the need for high temperature hydrogen
annealing.
[0055] Referring to FIG. 6, the method includes placing a substrate
(e.g., copper foil) in a processing chamber (610). In an
embodiment, the processing chamber is a quartz tube with an inside
diameter of 10 mm and an outside diameter of 12.5 mm. The method
also includes placing the processing chamber under vacuum, for
example, a pressure less than or equal to 500 mTorr. (612). A flow
of a carrier gas (e.g., hydrogen) is introduced into the processing
chamber, for example, a flow rate of H.sub.2 of between 2 sccm and
5 sccm, for example, 2 sccm, and a flow of trace amounts of a
carbon source (e.g., methane) is added to the flow of the carrier
gas, for example, a flow rate of CH.sub.4 of 0.0008 sccm (i.e.,
0.04% of the hydrogen flow rate) (614). The pressure in the
processing chamber is stabilized at a predetermined value, for
example, less than or equal to 500 mTorr, and the method includes
initiating an RF plasma in the processing chamber (616), using, for
example, an input power of 40 W using an Evenson cavity, which can
create the RF plasma in the vicinity of the substrate. In some
embodiments, the amount of the carbon source is a small fraction of
the gas flow, for example, less than 0.6%, for example, between
0.01% and 0.6%. In some implementations, the amount of the carbon
source is greater than 100 ppm. Thus, embodiments of the present
invention provide an RF plasma of hydrogen containing trace amounts
of methane as a carbon source. In addition to Evenson cavities,
other plasma sources can be utilized according to embodiments of
the present invention, for example, inductively coupled plasma
sources or the like. The gases in the plasma can also be varied,
for example, a plasma including argon ions, a plasma including
chlorine ions and methane-based radicals, combinations thereof,
such as chlorine, argon, and methane, and the like. Moreover,
heated wire (e.g., hot wire) filament techniques can be used to
create reactive species suitable for graphene growth in a process
analogous to the plasma-based graphene growth techniques discussed
herein. Combinations of plasma techniques and heated wire filament
techniques are also included within the scope of the present
invention.
[0056] In addition to the use of hydrogen as the carrier gas, other
carrier gases can be utilized, including nitrogen, argon, other
noble gases, chlorine, other halogens, mixtures of these gases
(e.g., chlorine and argon), and the like. In addition to the use of
methane as the carbon source, other gases can be utilized,
including acetylene (ethane, C.sub.2H.sub.2), 2,2-dimethylpropane
(neopentane, C.sub.5H.sub.12), allene (propadiene--C.sub.3H.sub.4),
ethane (C.sub.2H.sub.6), 1,2-butadiene (C.sub.4H.sub.6), ethyl
acetylene (1-butane--C.sub.4H.sub.6), 1,3-butadiene
(C.sub.4H.sub.6), ethylene (ethene--C.sub.2H.sub.4), isobutane
(2-methylpropane--C.sub.4H.sub.10), n-hexane (C.sub.6H.sub.14),
n-butane (C.sub.4H.sub.10), 1-butene (C.sub.4H.sub.8), methyl
acetylene (propane--C.sub.3H.sub.4), cis-2-butene (C.sub.4H.sub.8),
isopentane (2-methylbutane or 3-methylbutane--C.sub.5H.sub.12),
trans-2-butene (C.sub.4H.sub.8), n-pentane (C.sub.5H.sub.12),
isobutylene (2-methylpropane--C.sub.4H.sub.8), propane
(C.sub.3H.sub.8), cyclopropane (C.sub.3H.sub.6), propylene
(propene--C.sub.3H.sub.6), dimethylacetylene
(2-butane--C.sub.4H.sub.6), toluene (C.sub.7H.sub.8), dimethyl
ether (C.sub.3H.sub.6O), vinyl acetylene, or the like.
[0057] The method further includes subjecting the substrate to the
RF plasma for a predetermined period of time, for example, 15
minutes (618), during which the flow of the carrier gas and the
carbon source are continued while still operating at a reduced
pressure. In some embodiments, a fan or other cooling device (e.g.,
flowing air cooled by flowing through a tube having liquid
nitrogen) was applied to the region of the processing tube in which
the RF plasma is formed, reducing the temperature of the processing
environment, for example, to temperatures less than room
temperature. As an example, such cooling can reduce the temperature
of the outside of the processing chamber (i.e., the quartz tube) to
90.degree. C. or other comparable temperatures. Thus, embodiments
of the present invention may refer to room temperature growth of
the graphene film, but the present invention is not specifically
limited to growth at 24.degree. C., but can include other
comparable temperatures. Thus, room temperature, for the purposes
of this disclosure, is intended to include processing environments
in which there is no external heating of the substrate other than
heat that can be generated as a result of the RF plasma process. In
fact, as discussed above, cooling of the substrate and the region
of the processing chamber adjacent the substrate can be used to
remove a portion or all of the heat generated during the RF plasma
process.
[0058] In the method illustrated by FIG. 6, the addition of trace
amounts of methane or other carbon sources to the hydrogen plasma
can create reactive carbon species such as C.sup.+, CH.sup.+,
CH.sub.2.sup.+, and CH.sub.3.sup.+ in the plasma. These reactive
species, in addition to atomic hydrogen, result in the deposition
of graphene on the substrate as the simultaneous removal of copper
oxide and the deposition of graphene occurs. Without limiting
embodiments of the present invention, the inventor believes that
the graphene growth process includes the concurrent or simultaneous
removal of the copper oxide from the substrate surface, which
exposes the substrate surface to the reactive carbon species that
catalyze on the surface, leaving a graphene layer.
[0059] After formation of the graphene layer, the plasma is
extinguished, the processing chamber is back-filled with argon to
atmospheric pressure, and the substrate is removed from the
processing chamber. The inventor has noted that a the process
illustrated in FIG. 6, a significant amount of copper is observed
in the vicinity of the microwave cavity as a consequence of the RF
plasma removing the native copper oxide layer originally present on
the substrate surface.
[0060] It should be appreciated that the specific steps illustrated
in FIG. 6 provide a particular method of growing graphene according
to an embodiment of the present invention. Other sequences of steps
may also be performed according to alternative embodiments. For
example, alternative embodiments of the present invention may
perform the steps outlined above in a different order. Moreover,
the individual steps illustrated in FIG. 6 may include multiple
sub-steps that may be performed in various sequences as appropriate
to the individual step. Furthermore, additional steps may be added
or removed depending on the particular applications. One of
ordinary skill in the art would recognize many variations,
modifications, and alternatives.
[0061] FIG. 7 shows data for a graphene film grown using
conventional techniques and for a graphene film grown using an
embodiment of the present invention. As illustrated in FIG. 7, plot
A illustrates the Raman spectra for a conventional growth process
performed at 1,000.degree. C. Plot B illustrates the Raman spectra
for the single step, room temperature growth process described in
relation to FIG. 6. Plot B illustrates the Raman spectra for the
single step, room temperature growth process described in relation
to FIG. 6. Both films were grown on single crystal copper. The two
features of the Raman spectra at .about.1580 and 2700 cm.sup.-1 and
the absence of a pronounced defect peak at .about.1350 cm.sup.-1
indicate that both films are of good quality.
[0062] FIG. 8 is a simplified schematic diagram of a continuous
roll-to-roll system for graphene production according to an
embodiment of the present invention. As illustrated in FIG. 8, the
roll-to-roll system for producing graphene includes a roll of
copper foil 810 that is subjected using processing element 815 to a
plasma (e.g., an RF hydrogen plasma) either followed by or
concurrent with a gas jet of methane to form a layer of graphene.
The copper foil with graphene is then rolled onto the output roll
820. Using the embodiment illustrated in FIG. 8, the roll-to-roll
process can be used for continuous production of large area
graphene films. A reduced pressure atmosphere is provided at least
in the processing region but can also include the rolls of either
or both copper foil and copper foil with graphene. It will be
appreciated that the roll-to-roll process illustrated in FIG. 8 is
applicable to one or more of the methods of graphene production
described herein. In FIG. 8, graphene is illustrated as formed on
the front surface of the copper foil, however, it will be
appreciated that the graphene can be formed on the back surface of
the copper foil or both surfaces, depending on the particular
implementation. Additionally, a support or capping structure can be
used to modify the residence time of the species and/or precursors
adjacent the growth surface.
[0063] Although FIG. 8 illustrates a roll-to-roll process using
copper foil substrates and methane as the carbon source, other
substrates and carbon sources, as described throughout the present
specification, are included with the scope of the system
illustrated in FIG. 8. One of ordinary skill in the art would
recognize many variations, modifications, and alternatives.
[0064] It is also understood that the examples and embodiments
described herein are for illustrative purposes only and that
various modifications or changes in light thereof will be suggested
to persons skilled in the art and are to be included within the
spirit and purview of this application and scope of the appended
claims.
* * * * *